WO2008014965A1

WO2008014965A1 - Use of aminoacetones and salts thereof as bleaching boosters for peroxygen compounds

Info

Publication number: WO2008014965A1
Application number: PCT/EP2007/006742
Authority: WO
Inventors: Gerd Reinhardt; Georg Borchers; Michael Seebach
Original assignee: Clariant Finance (Bvi) Limited
Priority date: 2006-08-04
Filing date: 2007-07-31
Publication date: 2008-02-07
Also published as: DE102006036889A1; US20090289221A1; JP2010526156A; EP2049643A1

Abstract

The use is claimed of aminoacetones or salts thereof of the general formulae (I) and (II) in which R1 and R2 are each independently hydrogen, C1-C22-alkyl, C2-C22-alkenyl, phenyl or C5-C8-cycloalkyl, or R1 and R2 together with the nitrogen atom form a 5-, 6- or 7-membered ring system, X- is an anion, for example chloride, bromide, iodide, toluenesulfonate, benzenesulfonate, cumenesulfonate, mesitylsulfonate, sulfate, hydrogensulfate, acetate, fatty acid anion or anion of polycarboxylates, as a bleaching booster for inorganic peroxygen compounds in the pH range from 7 to 9.

Description

description

Use of aminoacetones and their salts as bleaching force enhancers for peroxygen compounds

The present invention relates to the use of certain aminoacetones and their salts for enhancing the bleaching effect of peroxygen compounds in the bleaching of dyed soils on textiles as well as on hard surfaces, as well as solid and liquid detergents and cleaners containing such aminoacetones or their salts.

So-called chlorine bleaching, which is based on the bleaching effect of hypochlorite or other active chlorine-containing compounds and is used both for textile bleaching and for hard surfaces, is widespread to this day. The high required for effective bleaching effect

Hypochlorite concentration, however, leads to severe color damage and may result in repeated use fiber damage.

For a long time, inorganic peroxygen compounds have been used as oxidizing agents for disinfecting and bleaching purposes. Typical examples include hydrogen peroxide and solid peroxygen compounds such as sodium perborate and sodium carbonate perhydrate which dissolve in water to release hydrogen peroxide. The oxidation effect of the peroxygen compounds is strongly temperature-dependent, a sufficiently fast bleaching is achieved only at temperatures above 80 ⁰ C. The oxidation effect of inorganic peroxygen compounds can be improved by addition of so-called bleach activators, so that even at temperatures around 60 ⁰ C substantially the same bleaching result is achieved as with the peroxide solution alone at 95 ° C. Examples of bleach activators are compounds from the group of N- and O-acyl compounds, such as polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), tetraacetylglucouril (TAGU), N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and Cyanurate, as well Carboxylic anhydrides, in particular phthalic anhydride and substituted maleic anhydrides, carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate (NOBS), sodium isononanoyloxybenzenesulfonate (ISONOBS) and acylated sugar derivatives, such as pentaacetylglucose (PAG).

At washing temperatures below 60 ⁰ C, especially below 45 ° C up to the cold water temperature, the effect of the previously known bleach activators often decreases. Another significant disadvantage of said bleach activators is their limited effectiveness in the pH range <9. Since their activation requires a high concentration of perhydroxyl anions, known activators preferably work best between pH 9 and 11. However, this results in deficits in certain fields of application, for example in liquid detergents or neutral or low-alkaline detergents and cleanser formulations.

There has been no lack of efforts to develop more effective bleaches without a convincing success to date. Thus, numerous metal-containing bleach catalysts are described in the literature, which are used together with peroxides. The use of metal-containing bleach catalysts, however, often has the disadvantage that damage to the textile fabric and the dyes used can occur.

No. 3,822,114 describes metal-free bleaching agents which, in addition to an organic or inorganic peroxygen compound, contain cyclic and open-chain aldehydes and ketones as bleach boosters. These systems allow a good oxidation effect at temperatures above 25 ° C. Other bleaching enhancers are i.a. in WO 95/31527 (bicyclic and tricyclic ketones such as decalin-1, 5-dione, methyldecalin-1, 6-dione and tricycloundecanedione) and in EP 1 209 221 (sugar ketones). US 5,785,887 protects the use of cyclic and open chain monoketals of diketones, e.g. Cyclohexanedione as

Bleach activators. Neither WO 95/31527, US 3,822,114 nor US 5,785,887 discloses aminoacetones or their salts as bleach boosters. The object of the invention is to improve the oxidizing and bleaching action of inorganic peroxygen compounds, in particular in the temperature range from 10 ⁰ C to 45 ° C and pH values in the range 7 to 9

Surprisingly, it has now been found that certain aminoacetones and their salts significantly improve the cleaning performance of inorganic peroxygen compounds on colored stains which are on textiles and on hard surfaces. Surprisingly, it has also been found that the best purification results of these aminoacetones and their salts are at a pH in the range of 7 to 9.

The invention relates to the use of aminoacetones or their salts of the general formulas (I) and (II)

R1. ~ - - XH,

N (I)

I Il

R2 O

wherein R ¹ and R ² independently of one another are hydrogen, C ₁ -C ₂₂ -alkyl, C ₂ -C ₂₂ -alkenyl-phenyl or C ₅ -C ₈ -cycloalkyl or R ¹ and R ² together with the nitrogen atom are a 5, 6 or 7-membered one X ^"is an anion, preferably chloride, bromide, iodide, toluenesulfonate, benzenesulfonate, cumene sulfonate, mesityl sulfonate, sulfate, hydrogensulfate, acetate, a fatty acid anion or an anion of polycarboxylates, especially fatty acids Anions of C ₈ -C ₂₂ - Anions of polycarboxylates are preferably anions of polyacrylic acid or of copolymers of maleic anhydride and acrylic acid.

Since the aminoacetones, in particular those which are liquid with short-chain radicals R ¹ and R ² , are highly volatile compounds, they are preferably in the form of their salts are used, for better handling, they are adsorbed in a particular embodiment on a solid support material.

Syntheses of corresponding aminoacetones are described in R. Stoermer et al., Chem. Ber., 28, 1895, 2220-2227 and Chem. Ben, 29, 1896, 866-874, in J. Magge and H. Henze, J. Amer. Chem. Soc., 60, 1938, 2148-2151, in J. King and McMillan, J. Amer. Chem. Soc., 73, 1951, 4451-4453 and H. Zaugg and B. Horrom, J. Amer. Chem. Soc., 72, 1950, 3004-3007. The synthesis is usually carried out by reacting a dialkylamine with monohalogenacetone in a solvent. Salts are formed by reacting the aminoacetone with an inorganic or organic acid. Preferred acids are hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, acetic acid, lauric acid, benzoic acid or polymeric carboxylic acids such as acidic or partially neutralized polyacrylic acids and copolymers of acrylic acid and maleic acid.

Particularly preferred Aminoacetone or their salts are: N, N-dimethylaminoacetone, N ₁ N- diethylaminoacetone, NN-Dipropylaminoaceton, N, Nn-Dibutylaminoaceton and N, N-Diisobutylaminoaceton, Piperidylaceton, 1-morpholin-4-yl-acetone, and N, N-dimethylaminoacetone hydrochloride, N, N-diethylaminoacetone hydrochloride, N, N-diethylaminoacetone hydrogensulfate, N, N-diethylaminoacetone acetate, N, N-diethylaminoacetone polycarboxylate, N, N-dipropylaminoacetone hydrochloride, N, N- Di-n-butylaminoacetone hydrochloride, N, N-diisobutylaminoacetone hydrochloride, piperidylacetone hydrochloride, and i-morpholino-1-yl-acetone hydrochloride.

The aminoacetones or their salts can be used either individually or in a mixture.

The aminoacetones and their salts can be used both with and without the use of a carrier for use in detergents and cleaners. In powdery or tableted products, the use of the aminoacetones or their salts on carrier materials is preferred as compounds. Examples of suitable carrier materials include clays, silicates, carbonates, phosphates, sulfates and citrates. Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, saponites, hectorites, smectites such as montmorillonite, in particular bentonites, bauxite and zeolites. Suitable are crystalline layered alkali metal silicates of the formula MM'SiχO ₍₂ xi ₎ ^* yH ₂ O (M ₁ M ¹ = Na, K, H, x = 1, 9-23, y = 0-25), preferably sodium silicates, for example below the trade name SKS-6 and Nabion ^® 15 available types. Also suitable are zeolites of type A and P.

Particularly suitable are bentonites such as are commercially available under the name Copisil® S 401, Copisil® N 401, Laundrosil® DGA, Laundrosil® EX 0242, Copisil® S 401, Copisil® N 401 or Ikomont® CA. Sheet silicates can also be used in acid-modified form, as are available in the commercial products Tonsil® EX 519, Tonsil Optimum 210 FF, Tonsil Standard 310 FF and 314 FF, and Opazil® SO from the company Südchemie.

Amorphous polysilicic acids whose internal surface is preferably in the range from 10 m ² / g to 500 m ² / g, in particular 100 m ² / g to 450 m ² / g, may furthermore be suitable as the carrier material. Suitable silicas are those which have been produced after the thermal process (flame hydrolysis of SiCl ₄ ) (so-called pyrogenic silicic acids) and silicas produced by wet processes (so-called precipitated silicas). They can also be prepared by the action of mineral acids on water glass.

Other particularly suitable support materials are sodium or potassium sulfates, sodium carbonates and sodium bicarbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate,

Pentasodium triphosphate, so-called sodium hexameta phosphate, oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and mixtures of sodium and potassium salts. D

Useful organic support materials are, for example, the carboxylic acids preferably used in the form of their sodium salts, such as citric acid, nitriloacetate (NTA) and ethylenediaminetetraacetic acid. Analogously, it is also possible to use polymeric carboxylates and their salts. These include, for example, the salts of homopolymeric or copolymeric polyacrylates,

Polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those of 50% to 10% of maleic acid, polyaspartic acid and also polyvinylpyrrolidone and urethanes. The molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid. In particular, water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a molecular weight of more than one million are also suitable. Examples of these are the polymers available under the name Carbopol 940 and 941.

In a particular embodiment, the salts of the aminoacetones according to the invention can be prepared in situ, e.g. by spraying the aminoacetone on an acidic or partially neutralized support (e.g., polyacrylic acid).

The compounds according to the invention consist of 20 to 98 wt .-%, preferably 30 to 95 wt .-%, particularly preferably 40 to 90 wt .-% of carrier material, the remainder is the aminoacetone or its salt, optionally also further aids.

In a further preferred embodiment, these powdery compounds may be in granulated form. Suitable binders for the granulation may include cellulose and starch and their ethers or esters, for example carboxymethylcellulose (CMC), methylcellulose (MC) or

Hydroxyethyl cellulose (HEC) and the corresponding starch derivatives, but also film-forming polymers, for example polyacrylic acids and copolymers of maleic anhydride and acrylic acid, and the salts of these polymer acids. Commercially available products are, for example, Sokalan® CP 5 or 45, Sokalan® CP 12 S or CP 13 S.

As binders and granulating agents and surfactants, in particular anionic and nonionic surfactants, surfactant compounds, di- and

Polysaccharides, cyclodextrins, fusible polyesters, polyalkylene glycols, in particular polyethylene, polypropylene glycols, particularly preferably polyethylene glycols having molecular weights of from 1000 to 10,000, preferably from 3,000 to 6,000, particularly preferably 4,000, fatty acids, in particular saturated fatty acids, such as lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated Erucic acid and behenic acid, and in particular from natural fatty acids, eg Coconut, palm kernel or Taigfettsäuren derived mixtures, soaps, in particular saturated fatty acid soaps and waxes are used.

The amount of auxiliaries, likewise based on the finished bleach compound, can be from 0 to 45% by weight, preferably from 2 to 20% by weight.

In a preferred embodiment, the mixture is initially introduced into the pulverulent carrier material in a mixer, preferably a plowshare mixer or intensive mixer, and charged with an aqueous aminoacetone or aminoacetone salt solution.

This results in a function of the concentration of the solution, the carrier used and the process parameters, a specific loading limit. Typically, loadings of about 20-70 wt .-% solution (based on proportion in the total compound) can be achieved. Following the granulation, the moist product is dried, preferably fluidized bed or fluidized bed dryers are used. After drying, granules are obtained which typically have an active content of 10-60% aminoacetone or aminoacetone salt. From the granules produced by segregating the coarse grain and the fine grain fraction are separated. The coarse grain fraction is crushed by grinding and just like the

Fine grain content fed to a renewed granulation process. The grain size of the granules produced in this way is generally in the range of 50 to 2000 microns, preferably 150 to 1800 microns, more preferably from 300 to 1500 microns.

In a further embodiment, after the aqueous aminoacetone or aminoacetone salt solution has been applied to the support material, a

Form granulation of the mixture by dies in the extruder, but also by ring roller presses, edge runner be performed. Here, the carrier material is to be selected and the loading concentration adjusted so that the mixture has a sufficient plastic deformability. Optionally, the extrudates obtained from the process may be rounded in a raking apparatus. Finally, the granules are dried and worked up in an analogous manner as described above.

In another preferred embodiment, the aminoacetone or aminoacetone salt solution is sprayed onto the carrier material in a fluidized-bed granulation process and granulated. Since the process offers the advantage of simultaneous granulation and drying, higher loadings can usually be achieved compared to a sequential process of carrier in the mixer with subsequent drying. The loading limit is then determined by the physical properties of the individual components or of the mixture.

The granules obtained according to the invention are suitable directly for use in detergents and cleaners. In a particularly preferred form of use, however, they can be provided with a coating shell according to methods known per se. For this purpose, the granules are coated in an additional step with a film-forming substance, whereby the product properties can be significantly influenced.

Suitable coating agents are all film-forming substances, such as waxes, silicones, fatty acids, fatty alcohols, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, anionic and cationic polymers, and polyalkylene glycols. Preference is given to coating substances with a Melting point of 30 - 100 ⁰ C used. Examples of these are: C ₈ -C ₃₁ fatty acids, for example lauric, myristic, stearic acid; Cβ-CarFettalkohole; Polyethylene glycols having a molecular weight of 1000 to 50,000 g / mol; Fatty alcohol polyalkoxylates with 1 to 100 moles EO; Alkanesulfonates, alkylbenzenesulfonates, α-olefinsulfonates, alkyl sulfates, alkyl ether sulfates having C 8 -C 31 -hydrocarbon radicals, polymers, for example polyvinyl alcohols, waxes, for example montan waxes, paraffin waxes, ester waxes, polyolefin waxes, silicones.

In the coating substance which softens or melts in the range from 30 to 100 ^° C., further substances which do not soften or melt in this area can be present in dissolved or suspended form, for example homopolymers, copolymers or graft copolymers of unsaturated carboxylic acids and / or sulfonic acids and their derivatives Alkali salts, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone; mono- and polyvalent carboxylic acids,

Hydroxycarboxylic acids or ether carboxylic acids having 3 to 8 C atoms and their salts; Silicates, carbonates, bicarbonates, sulfates, phosphates, phosphonates. Depending on the desired properties of the coated granules, the content of coating substance can be from 1 to 30% by weight, preferably from 5 to 15% by weight, based on the coated granules.

For applying the coating substances, mixers (mechanically induced fluidized bed) and fluidized bed apparatuses (pneumatically induced fluidized bed) can be used. As mixers, for example, plowshare mixers (continuous and batchwise), ring layer mixers or even Schugi mixers are possible. The tempering can be carried out using a mixer in a granule preheater and / or in the mixer directly and / or in a fluidized bed downstream of the mixer. Granulated coolers or fluid bed coolers can be used to cool the coated granules. In the case of fluidized bed apparatuses, the heat treatment takes place via the hot gas used for fluidization. The granules coated by the fluidized-bed method can be cooled by a granulate cooler or a fluidized-bed cooler, similar to the mixing method. Both in the mixing process and in the fluidized bed process can the coating substance be sprayed on a single-material or a Zweistoffdüsvorrichtung. The optional tempering consists in a heat treatment at a temperature of 30 to 100 ⁰ C, but equal to or below the melting or softening temperature of the respective shell substance. Preference is given to working at a temperature which is just below the melting or softening temperature.

The bleaching compounds according to the invention are distinguished by very good storage stability in pulverulent washing, cleaning and disinfecting agent formulations. They are ideal for use in heavy-duty detergents, stain salts, machine dishwashing detergents and powdery all-purpose cleaners.

The aminoacetones or their salts are used in the detergents and cleaners according to the invention which additionally also contain organic or inorganic peroxygen compounds in concentrations of from 0.01 to 10%, preferably from 0.1 to 8% and in particular from 0.5 to 5%.

As the peroxygen compound, all alkali metal or ammonium peroxosulfates are primarily considered, e.g. potassium peroxymonosulfate

(technically: Caroat® or Oxone®). For use in alkaline powdered formulations, it is advantageous that potassium peroxomonosulfate (usually in the form of the triple salt) in the form of granules such as e.g. in DE 196 46 225 are described in order to increase their storage stability. In addition, however, it is also possible to use alkali perborate monohydrate or tetrahydrate and / or alkali metal percarbonate, with sodium being the preferred alkali metal. The concentration of the inorganic oxidizing agents on the total formulation of the cleaning agents is 1 to 90%, but preferably 5 to 25%.

Additionally or alternatively, the cleaning agents according to the invention may contain organic-based oxidizing agents in the concentration range from 1 to 20%. These include all known peroxycarboxylic acids, such as Monoperoxyphthalic acid, dodecanediperoxyacid or phthalimidoperoxycarboxylic acids such as PAP.

The term bleaching is understood here to mean both the bleaching of dirt located on the textile surface and the bleaching of dirt located in the wash liquor and detached from the textile surface. The same applies analogously to the bleaching of stains on hard surfaces. Other potential applications are in the personal care field, e.g. to improve the effectiveness of denture cleaners. Furthermore, find the complexes of the invention

Use in commercial laundries, in wood and paper bleach, bleached cotton and in disinfectants.

Furthermore, the invention relates to a washing and cleaning agent such as detergents and bleaches for textile materials, cleaning agents for hard surfaces such as dishwashers or denture cleaners containing the aminoacetones or their salts as defined above and peroxygen compounds.

The use of the aminoacetones and their salts as bleach catalysts consists essentially in the presence of a colored with

Soiling of contaminated hard surface or a correspondingly soiled textile conditions under which a peroxidic oxidizing agent and the aminoacetone or an aminoacetone salt can react with the aim of producing more strongly oxidizing secondary products, e.g. with dioxirane structure. Such conditions are especially present when the reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the aminoacetone or its salt to a washing or detergent-containing solution. From the beginning, the cleaning or washing agent particularly advantageously contains the aminoacetone or a

Aminoacetonsalz and optionally a peroxygen-containing oxidizing agent. The peroxygen compound may also be used separately in bulk or as preferably aqueous solution or suspension may be added to the solution when a non-oxygen detergent or cleaning agent is used.

The detergents and cleaning agents according to the invention, which may be in the form of granules, powdered or tablet-like solids, other shaped articles, homogeneous solutions or suspensions, may in principle contain all known and conventional ingredients in addition to the aminoacetones and their salts mentioned.

The detergents and cleaners according to the invention may contain, in particular, builder substances, surface-active surfactants, sequestering agents, enzymes and also special additives with a dye-protecting or fiber-sparing action. Other adjuvants such as electrolytes, foam regulators and dyes and fragrances are possible.

In order to establish a desired pH, which does not naturally result from the mixture of the other components, the compositions according to the invention may contain system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali metal hydrogensulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the compositions according to the invention. contain.

Examples

Comparative example: Synthesis of N, N, N-diethylmethylammonium acetone tosylate

19.4 g (0.15 mol) of N, N-diethylaminoacetone were dissolved in 70 ml of acetonitrile and the solution was treated within 10 min at 35 ° C with 27.9 g (0.15 mol) of p-toluenesulfonate and allowed to react for 24 h calmly. The clear solution was completely concentrated and the crude product recrystallized from i-propanol / acetic acid methyl ester. Yield: 41.3 g of white solid

Example 1: Synthesis of N, N-diethylaminoacetone

478 g (6.54 mol) of diethylamine were dissolved in 650 ml of diethyl ether. At 35 ° C., 302.4 g (3.27 mol) of chloroacetone were added dropwise with stirring over the course of 10 minutes. An initial slight haze intensified as chloroacetone was added. After 6 h at 45 ⁰ C, the resulting yellow-brown suspension was cooled and filtered off with suction at a temperature of 0 ⁰ C. The precipitated diethylamino hydrochloride was washed with diethyl ether, the filtrate was then concentrated in vacuo and cooled to ⁰ ° C. for 12 h. Recrystallized diethylamino hydrochloride was filtered off with suction and washed with a small amount of cold diethyl ether. The ethereal solution of diethylaminoacetone was completely concentrated in vacuo and the remaining brown oil fractionally distilled in vacuo. Boiling point 67 to 70 ° C (49 mbar).

Yield Diethylaminoacetone: 337 g (2.6 mol), 79.8%

The diethylamino hydrochloride formed as a by-product can be converted back into the free amine by addition of base and used for further experiments. Example 2: Synthesis of N, N-diethylaminoacetone hydrochloride

100 g (0.77 mol) of N, N-diethylaminoacetone were dissolved in 387 ml of water and the solution was added with stirring within 10 min with 1 N hydrochloric acid (774 ml, 0.77 mol). The reaction mixture was then completely concentrated in vacuo at 60 ⁰ C, the product was isolated in a yield of 99.5%.

Example 3: Neutralization of N, N-diethylaminoacetone with Sokalan® CP 45

5.0 g of N, N-diethylaminoacetone was dissolved in water to give a 50% aqueous solution. The pH of the solution was 10.1. Subsequently, 43.5 g of a 14.3% aqueous Sokalan solution were added with stirring and slight warming to 38 ° C, the pH was 7 after completion of the addition. The 14.3% Sokalan solution was prepared by dissolving 20.0 g of Sokalan® CP 45 in 120 ml of water. The reaction mixture was completely concentrated in vacuo at 60 ° C to isolate 9.8 g of the crystalline product with an active content of 44.6%.

Example 4: Neutralization of N, N-diethylaminoacetone with p-ToluoIsulfonsäure

1.29 g of N, N-diethylaminoacetone were dissolved in 5 ml of water. The pH of the solution was 10.1. Thereafter, 1.9 g of p-toluenesulfonic acid monohydrate were added, with stirring and slight heating to 28 ° C., the pH being 7 after the end of the addition. The reaction mixture was completely concentrated in vacuo at 60 ^° C. to give 3.3 g of an orange-colored resin which was subsequently crystallized in the refrigerator. 2.8 g of yellow-orange crystals were obtained.

Example 5: Synthesis of N, N-dipropylaminoacetone

202.38 g (2 mol) of dipropylamine were dissolved in 200 ml of diethyl ether. 92.53 g (1 mol) of chloroacetone were added at 35 ° C. with stirring within 10 minutes dropwise. An initial slight haze intensified as chloroacetone was added. After 6 h at 45 ° C, the resulting whitish-yellow suspension was cooled and filtered off with suction at a temperature of 0 ⁰ C. The precipitated dipropylamino hydrochloride was washed with diethyl ether, the filtrate was then concentrated in vacuo and cooled to 0 ⁰ C for 12 h. Once again crystallized dipropylamino hydrochloride was filtered off with suction and washed with a small amount of cold diethyl ether. The ethereal solution of Dipropylaminoacetons was completely concentrated in vacuo and the remaining brown oil fractionally distilled in vacuo. Boiling point 62 ° C (5 mbar). Yield: 123.1 g.

Example 6: Synthesis of N.N-dipropylaminoacetone hydrochloride

5 g (31.8 mmol) of N, N-dipropylaminoacetone were dissolved in 15.9 ml of water and the solution was stirred with 1N hydrochloric acid (31, 8 ml,

31, 8 mmol). The reaction mixture was then completely concentrated in vacuo at 60 ⁰ C, whereby the hygroscopic product was isolated in a yield of 98%.

Example 7: Synthesis of N, N-diisobutylaminoacetone

258.5 g (2 mol) of diisobutylamine were dissolved in 200 ml of diethyl ether. At 35 ⁰ C of chloroacetone were added dropwise with stirring within 10 min 92.53 g (1 mol). An initial slight haze intensified as chloroacetone was added. After 6 h at 45 ° C, the resulting whitish-yellow suspension was cooled and filtered off with suction at a temperature of 0 ⁰ C. The precipitated diisobutylamino hydrochloride was washed with diethyl ether, the filtrate was then concentrated under reduced pressure and cooled to ⁰ ° C. for 12 h. Recrystallized diisobutylamino hydrochloride was sucked off and washed with a small amount of cold diethyl ether. The ethereal solution of Diisobutylaminoacetons was completely concentrated in vacuo and the remaining brown oil fractionally distilled in vacuo. Boiling point 74 ° C (5 mbar). Yield: 86.9 g of colorless oil. Example 8: Synthesis of N, N-diisobutylaminoacetone hydrochloride

5 g (27 mmol) of NN-diisobutylaminoacetone were dissolved in 13.5 ml of water and the solution was added with stirring within 10 min with 1 N hydrochloric acid (27 ml, 27 mmol). The reaction mixture was then completely concentrated in vacuo at 60 ⁰ C, whereby the product was isolated in a yield of 85%.

Example 9: Synthesis of N, N-di-n-butylaminoacetone hydrochloride

5 g (27 mmol) of N, N-di-n-butylaminoacetone (prepared according to Example 7 from di-n-butylamine and chloroacetone) were dissolved in 13.5 ml of water and the solution was stirred with 1 N hydrochloric acid within 10 min (27 ml, 27 mmol). The reaction mixture was then completely concentrated in vacuo at 60 ⁰ C, the product was isolated in a yield of 95%.

Example 10: Synthesis of piperidylacetone

170.3 g (2 mol) of piperidine were dissolved in 200 ml of diethyl ether. At 35 ° C 92.53 g (1 mol) of chloroacetone were added dropwise with stirring over 10 min. An initial slight haze intensified as chloroacetone was added. After 6 h at 45 ° C, the resulting whitish-yellow suspension was cooled and filtered off with suction at a temperature of 0 ° C. The precipitated piperidine hydrochloride was washed with diethyl ether, the filtrate was then concentrated in vacuo and cooled to 0 ° C for 12 h. Once again crystallized piperidinyl hydrochloride was filtered off with suction and washed with a small amount of cold diethyl ether. The ethereal solution of piperidylaminoacetone was completely concentrated in vacuo and the remaining brown oil fractionally distilled in vacuo. Boiling point 60 ^° C. (5 mbar). Yield: 118.4 g of colorless oil. Example 11: Synthesis of piperidylacetone hydrochloride

5 g (36.7 mmol) of piperidylaminoacetone were dissolved in 18.4 ml of water and the solution was added with stirring within 10 min with 1 N hydrochloric acid (36.7 ml, 36.7 mmol). The reaction mixture was then completely concentrated in vacuo at 60 ⁰ C, whereby the hygroscopic product was isolated in a yield of 100%.

Example 12: pH dependence of the bleach (comparison of diethylaminoacetone, diethylaminoacetone hydrochloride and diethylmethylammonium acetone tosylate)

To determine the pH dependence of the bleaching of diethylaminoacetone or diethylaminoacetone hydrochloride according to Example 1 or Example 2, washing experiments were carried out in a beaker at 25 ° C. with a mechanical stirrer. For this purpose, 2 g / l of standard detergent IEC A (wfk Krefeld) were dissolved in 400 ml of water with a hardness of 15 ° dH, 0.35 g / l of caroate and 0.04 g / l of the sample was added. After adjusting the pH with acid or base, 4 laps of test fabric BC-1 (tea on cotton, wfk Krefeld) were added in each case and the wash liquor was stirred for 60 min, while the pH was kept constant.

Before and after washing, the whiteness of the test soiling was determined by means of an Elrepho measuring instrument. As a result, the whiteness (dE) was represented as a function of the pH:

Sample pH 5 pH 7 pH 8 pH 9 pH 10 pH 11

Example 1 53.5 52.5 57.2 48.3 48.7 46.5

Example 2 53.6 51, 9 59.7 50.8 50.0 45.4

Caroat 48.3 8.5 47.6 48.0 48.2 47.8

Comparative Example 47.3 47.2 48.0 48.5 48.6 48.0

The results show a bleaching optimum of the ketones of the invention at pH 8 while the comparative compound, the quaternized aminoacetone none Has bleaching effect in this pH range. Likewise, bleaching without ketone addition (caroate only) is not pH dependent.

Example 13: Bleaching performance of dialkylaminoacetones and their salts

5 g / L of standard liquid detergent (pH 7.3) are dissolved in 200 ml of water (15 ° dH). 0.35 g / L caroate and 0.04 g / L of a dialkylaminoacetone or dialkylaminoacetone salt are added. 4 cloth test fabric BC-3 (tea on cotton, wfk-Krefeld) added and the washing test in a Linitestgerät the company out (Hanau) 30 min at 40 ⁰ C carried out. After the washing process, the cloths are washed out with water and dried. The remission is determined by means of an Elrepho whiteness measuring device. As a result, the remission difference of the sample washed with the above-mentioned bleaching system is reproduced in comparison with the test fabric washed only with liquid detergent.

Dialkylaminoacetone remission difference

Example 1 2.7

Example 5 4.1

Example 6 3.8

Example 7 4.0

Example 9 2.4

Example 10 2.8

Example 11 2.6 only caroate 1, 0

The results show that all tested dialkylaminoacetones act as performance boosters for caroate. If a standard powder detergent (pH 10.3) is used instead of the neutral liquid detergent, no bleach-enhancing effects are observed with the dialkylaminoacetones according to the invention. This demonstrates the effectiveness of the ketones of the invention in the claimed pH range <9. Example 14: Mixer granulation of diethylaminoacetone hydrochloride

In a laboratory mixer, 61.7 g of the acid-modified Bentonite Copisil S 401, with a solids content of about 81%, and charged with 41, 6 g of a 50% aqueous solution of Diethylaminoacetonhydrochlorids loaded. The resulting wet product is then transferred to a laboratory fluidized bed dryer (Retsch TG 100 type). The material is dried for 20 min at T = 50 ⁰ C and then screened out the granulate fraction 315 - 1250 microns. The granules thus obtained have an active ingredient content of about 29.4% Diethylaminoacetonydrochlorid.

Claims

claims

1. Use of aminoacetones or their salts of the general formulas (I) and (II)

in which R ¹ and R ^2, independently of one another, denote hydrogen, C ¹ -C 22 -alkyl, C ₂ -C _{2 2} -alkenyl, phenyl or C ₅ -C ₈ -cycloalkyl or R ¹ and R ² together with the nitrogen atom denote a 5, 6 or 7 form a ring system, and X ^" denotes an anion, as a bleaching force enhancer for inorganic peroxygen compounds in the pH range 7 to 9.

2. Use of aminoacetones or salts thereof according to claim 1, characterized in that as aminoacetones or their salts, the compounds:

N, N-diethyaminoacetone (III)

^C 2 ^H 5 ^ _N ^ / ^CH 3 (III)

C ₂ H ₅ O

N, N-diethylaminoacetone hydrochloride (IV)

be used.

3. Bleaching systems consisting essentially of an aminoacetone or its salt according to claim 1 and an inorganic peroxygen compound.

4. Bleaching systems according to claim 3, characterized in that they contain as peroxygen compound alkali metal or ammonium peroxomonosulfate or mixtures thereof with alkali perborate mono- or tetra hydrate and / or alkali metal percarbonates.

5. bleaching compounds consisting essentially of a carrier material to which an aminoacetone or its salt according to claim 1 is applied.

6. bleaching compounds according to claim 5, characterized in that it contains 40 to 90 wt .-% of carrier material and 10 to 60 wt .-% aminoacetone or its salt.

7. bleaching compounds according to claim 5, characterized in that it contains additional binders and / or granulation aids.

8. A process for the preparation of the bleaching compounds according to claim 5, characterized in that one mixes the components a), b) and optionally c) and optionally granulated and dried this mixture.

9. washing, bleaching and cleaning agent containing an aminoacetone or its salt according to claim 1.

10. washing, bleaching and cleaning agent containing a bleaching compound according to claim 5.